CN106893545A - 用于电容去离子电极的粘结剂与其形成方法 - Google Patents
用于电容去离子电极的粘结剂与其形成方法 Download PDFInfo
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Abstract
本发明提供用于电容去离子电极的粘结剂及其形成方法。所述粘结剂是由疏水性的聚醚多元醇、二异氰酸酯、与具有疏水性侧链的二醇反应而成。上述粘结剂可粘结活性材料，以形成电容去离子电极。活性材料与粘结剂的重量比可介于90:5至90:25之间。
Description
技术领域
本发明是关于电极的粘结剂，更特别关于用于电容去离子电极的粘结剂，及其形成方法。
背景技术
碳电极在制备的过程中常需使用高分子粘结剂(polymer binder)，用以粘结电极材料颗粒并固定电极材料颗粒与集电板(current collector)。高分子粘结剂接合的效果对电极的功能影响甚巨，故高分子粘结剂特性的调控非常重要。一般电极制备常使用氟系高分子作为粘结剂，其中以PVDF(polyvinylidenefluoride)最为普遍。PVDF粘结剂可形成化学安定网络结构(chemically inertnetwork)，其机械强度可有效且大范围支撑活性材料颗粒间的相互连结，于适当用量下不会影响到活性材料的电化学特性。然而PVDF粘结剂具有成本高、可挠性(flexibility)低、及环境友善性低等缺点。
综上所述，目前亟需新的粘结剂组成取代PVDF粘结剂，以用于粘结电极材料颗粒并将其固定至集电板。
发明内容
本发明的目的在于提供一种可取代PVDF粘结剂、用于电极的新型粘结剂，以用于粘结电极材料颗粒并将其固定至集电板。
本发明一实施例提供的用于电容去离子电极的粘结剂，包括：具有疏水性的聚醚多元醇、二异氰酸酯、与具有疏水性侧链的二醇反应而成的产物。
本发明一实施例提供的用于电容去离子电极的粘结剂的形成方法，包括：混合疏水性的聚醚多元醇、二异氰酸酯、与具有疏水性侧链的二醇，反应形成粘结剂。
本发明的优点在于：本发明利用具有疏水性的聚醚多元醇、二异氰酸酯与具有疏水性侧链的二醇反应而成的产物(聚氨酯)作为粘结剂，该聚氨酯在干燥时，具有良好热稳定性、高化学稳定性、且能被电解质湿润，因此含有上述聚氨酯作为粘结剂的电极具有多种用途，例如：上述电极可搭配对电极与两者之间的水相溶液以作电容去离子之用，或将上述聚氨酯作为粘结剂的电极用于其他诸如锂电池、燃料电池、超级电容器或储氢装置等的装置中。
附图说明
图1A是不同分子量的PU电极的虚部阻抗对实部阻抗的曲线图；
图1B是图1A的部份放大图；
图2是不同分子量的PU电极的相角对频率的曲线图；
图3A是PU电极与PVDF电极的虚部阻抗对实部阻抗的曲线图；
图3B是图3A的部份放大图；
图4是PU电极与PVDF电极的相角对频率的曲线图。
具体实施方式
本发明一实施例提供的聚氨酯，是由1摩尔份的疏水性的聚醚多元醇(HO-R2-OH)、3至20摩尔份的二异氰酸酯(ONC-R1-NCO)、与1至6摩尔份的具有疏水性侧链的二醇(HO-R3-OH)反应而成。上述反应如式1所示：
在式1中，R1、R2、与R3取决于二异氰酸酯、疏水性的聚醚多元醇、与具有疏水性侧链的二醇的种类，而x与y取决于疏水性的聚醚多元醇与具有疏水性侧链的二醇的摩尔比例。
另一方面，聚氨酯为无规共聚物，即上述对应x的重复单元与对应y的重复单元的排列方式为无规。
在一实施例中，疏水性的聚醚多元醇种类的碳氢主链(hydrocarbonbackbone)为具高挠曲性与疏水特性，而具有疏水性侧链的二醇种类则为控制链段软硬程度，以及侧链疏水增加粘结剂防水性。
在一实施例中，聚氨酯的数目平均分子量大于1.6×105以上。若聚氨酯的数目平均分子量过低，则无法有效粘结活性材料以作为电极。若聚氨酯的数目平均分子量过高，则粘度(viscosity)过高且结构弹性(elasticity)过低，不利于配制电极浆料并降低电极效能。
举例来说，二异氰酸酯可为六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、或上述的组合。
疏水性的聚醚多元醇可为聚丁二醇、聚丙二醇、或上述的组合。疏水性的聚醚多元醇的挠曲性高且具疏水特性。在一实施例中，聚醚多元醇的数目平均分子量介于1000至5000之间。若疏水性的聚醚多元醇的数目平均分子量过低，分子结构会较硬及脆，不易服帖。若聚醚多元醇的数目平均分子量过高，则分子结构会较软，且内聚强度变弱。具有疏水性侧链的二醇可为C12-26的单脂肪酸甘油酯、C12-26的二聚脂肪酸(dimer acids)、或上述的组合。
具有疏水性侧链的二醇可作为聚氨酯的硬段，控制聚氨酯的软硬程度。另一方面，具有疏水性侧链的二醇的疏水侧链可增加聚氨酯的疏水性，且侧链碳数愈高则疏水性愈高。
在一实施例中，可混合90重量份的活性材料与5至25重量份的粘结剂如上述聚氨酯、与溶剂(如N-甲基吡咯烷酮(NMP)、异丙醇、乙醇、或上述的组合)以形成浆料。接着将浆料涂布于集电板(如铜、铝、钛、其他金属、或上述的合金)上烘干，即形成电极。若粘结剂的比例过低，则无法有效粘结活性及导电材料与集电板而有脱落问题。若粘结剂的比例过高，则可能会增加电极电阻而降低电极效能。举例来说，活性材料可为活性碳材、纳米碳管、石墨烯、或上述的组合等高比表面积的材料。上述活性材料的比表面积介于300m2/g至3000m2/g之间，且其孔洞大小介于1至1000nm。若活性材料的比表面积过小，则会影响电吸附离子容量。若活性材料导电度不足(如活性碳材料)，可添加5至20重量份的导电材料帮助导电，且导电材料可为石墨、碳黑、乙炔黑、或上述的组合。但值得注意的是，添加量过多(如石墨或碳黑)的导电材料，会使活性碳的材料重量比例含量下降，导致吸附离子的有效面积降低，进而使其吸附电容下降。
上述聚氨酯在干燥时，具有良好热稳定性、高化学稳定性、且能被电解质湿润，因此含有上述聚氨酯作为粘结剂的电极具有多种用途。在一实施例中，上述电极可搭配对电极与两者之间的水相溶液，以作电容去离子之用。在其他实施例中，上述聚氨酯作为粘结剂的电极可用于其他装置如锂电池、燃料电池、超级电容器、或储氢装置。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂，下文特举数实施例作详细说明如下：
实施例
实施例1
取1摩尔份的聚丁二醇(PTMEG，购自立大化工，数目平均分子量为2000)与3摩尔份的硬脂酸甘油酯(GMS)加入300mL的除水NMP中，加热至70℃形成均相溶液。接着将上述溶液降温至50℃后，将3摩尔份的甲苯二异氰酸酯(TDI)加入上述溶液，待温度稳定后再加热上述反应物至70℃并于70℃下反应。在反应3小时后，每隔一小时取样确认反应物中的-NCO官能基残留量，待-NCO官能基残留量不再降低后，可进一步添加溶剂稀释产物，再加入额外TDI以增加产物分子量。上述链延长反应可进行多次，即可得多种不同数目平均分子量的聚氨酯。PTMEG与TDI(起始用量与后续添加量的总合)的摩尔比介于1:6至1:16之间。聚氨酯产物依数目平均分子量高低可分为含6摩尔份TDI的PU(A)、含7摩尔份TDI的PU(B)、含8摩尔份TDI的PU(C)、含10.5摩尔份TDI的PU(D)、与含13.5摩尔份TDI的PU(E)，其数目平均分子量如表1所示。
秤取80重量份的活性碳(activated carbon，AC)作为活性材料、10重量份的石墨粉(购自EMAXWIN)作为导电材、与10重量份上述制备的聚氨酯溶液(15wt％，PU(A)至PU(E))作为粘结剂，均匀搅拌24小时使之成为糊状浆料。接着以涂布间隙300μm的刮刀将糊状物均匀涂布在50μm钛箔上，送入120℃烘箱中烘干4小时，完成PU电极。
比较例
秤取80重量份的活性碳(activated carbon，AC)作为活性材料、10重量份的石墨粉(购自EMAXWIN)作为导电材、与10重量份的聚偏二氟乙烯(Poly(vinylidene fluoride，PVDF)溶液(5wt％，数目平均分子量为534,000，购自Aldrich)作为粘结剂，均匀搅拌24小时使之成为糊状浆料。接着以涂布间隙300μm的刮刀将糊状物均匀涂布在50μm钛箔上，送入120℃烘箱中烘干4小时，完成PVDF电极。
粘结剂最基本的要求是对高比表面积活性材料、导电材料、与集电板有好的粘着性，利用万能拉力机测定活性碳涂层在钛集电板的剥离强度。将制备好的碳电极裁切为2.5cm宽的长条状，再将标准胶带粘上、并以2公斤滚轮来回压合3次，即可制备成T peel拉伸的样品，以万能拉力机定速率30cm/min测试剥离强度，荷重模头显示的力量数值即是剥离强度，单位为kg/25mm。上述粘结剂的剥离强度如表1所示。
表1、不同分子量PU粘结剂的剥离强度
较低分子量的PU(A)及PU(B)其分子特性较为软粘且不成膜，以致电极无法完整成膜，因此活性碳涂层在集电板上易剥离，活性碳分子之间作用力低。由剥离强度的结果也可看出，较低分子量的PU粘结剂接着强度差。随着PU粘结剂分子量提高，可看出PU(C)、(D)、(E)接着强度有提升趋势，由于分子量越大，PU弹性体所含极性胺基比例愈高，与碳材间的接着作用力愈佳，因而粘结剂展现的强度愈高、表面更不沾粘。如表1所示，某些PU粘结剂的接着强度优于PVDF。
接着以循环伏安法(cyclic voltammetry，CV)分析PU电极与PVDF电极的电容值。测试溶液为0.5M NaCl水溶液，工作电极面积1cm x 1cm，对电极为白金线，参考电极为氯化银电极(AgCl/Ag)，电位扫描范围为-0.5～0.5V，扫描速率为10mV/s，对CV曲线积分得到的电荷变化量，除以电位窗及电极活性材料重量即得电极的比电容值。
在剥离强度测试(peel test)中得知较低分子量的PU(A)及PU(B)会导致电极涂布的均匀性及接着强度差，以致电极无法完整成膜而无法测得比电容值。如表2所示，随着PU粘结剂分子量提高，可观察到电极涂布均匀性及接着强度有提升趋势(比电容值也从54.0F/g增加至91.1F/g)。由于高分子量的PU粘结剂可形成网状结构，可大范围包覆颗粒、藉由网状强度支撑使颗粒相互连结。较长的PU分子链可避免发生小分子粘结剂阻塞活性碳材孔洞结构，进而提高其比电容值。
表2
另外，利用交流阻抗频谱分析(electrochemical impedance spectroscopy,EIS)进行比较不同分子量的PU电极的阻抗特性，如图1A与图1B所示。图1B是图1A的部份放大图。在图1A与图1B中，纵轴读值为虚部阻抗(capacitanceimpedance)，而横轴读值为实部阻抗电阻值(resistance)。由图1A可知，采用高分子量的PU(E)作为粘结剂的电极，在中高频区域(半圆区间)所产生的阻值，比采用低分子量PU(C)及PU(D)作为粘结剂的电极低，因此具有较高的比电容值。而不同频率与相角的变化如图2所示，PU(E)电极在低频区域，其相角明显高于PU(C)及PU(D)电极，显示PU(E)电极较偏向电容反应。推估应是PU(E)的较长分子链不易深入活性碳材孔洞结构，降低孔洞被堵塞的情形，有助于减少碳电极的界面电阻。综上所述，PU(E)电极具有较高比电容值。
实施例2
固定活性碳与石墨粉的重量比为80:10，并调整PU粘结剂的添加重量比为5至20重量份，以确认PU粘结剂添加比例对电容的影响，如表3所示。结果显示当碳材、导电材与PU重量比为80:10:5的时候，碳电极接着性为中，而随着PU添加比例增加而提升至高，此外，不同PU添加比例的碳电极均匀性皆为高。在电容表现的方面，活性碳与PU粘结剂的重量比为80:10、80:15与80:20的电极比电容值相近，而以活性碳与PU粘结剂的重量比为80:15时有最高比电容值为101F/g，值得注意的是，在活性碳与PU粘结剂的重量比为80:5时，电极比电容值67.1F/g表现最低，推论原因当添加的PU粘结剂量过少时，会影响碳颗粒与集电板间有效的连结性，因此反而造成更大的界面电阻而使电容表现较差。
表3
实施例3
取PU(E)电极与PVDF电极进行循环伏安分析比较，如表4所示。结果显示PVDF电极的比电容值为87.3F/g，而PU(E)电极的比电容值为91.1F/g，优于PVDF电极。
表4
| 粘结剂 | 活性碳:石墨:粘结剂 | 电极均匀性 | 接着性 | 比电容值(F/g) |
| PU(E) | 80:10:10 | 高 | 高 | 91.1 |
| PVDF | 80:10:10 | 高 | 高 | 87.3 |
另外，利用交流阻抗频谱分析(electrochemical impedance spectroscopy,EIS)进行比较PU电极与PVDF电极的阻抗特性，如图3A与图3B所示。图3B是图3A的部份放大图。由图3A可知，采用PU(E)作为粘结剂的电极，在中高频区域(半圆区间)所产生的阻值，比采用PVDF作为粘结剂的电极低，因此具有较高的比电容值。而不同频率与相角的变化如图4所示，PU(E)电极在低频区域，其相角较PVDF电极接近90°，显示相较于PVDF电极，PU(E)电极较偏向电容反应，因此以PU(E)粘结剂制备电极的比电容值高于PVDF电极。综上所述，PU可取代PVDF作为电极中活性材料的粘结剂。
虽然本发明已以数个实施例发明如上，然其并非用以限定本发明，任何本技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作任意的更动与润饰，因此本发明的保护范围当视后附的申请专利范围所界定者为准。
Claims (20)
1.一种用于电容去离子电极的粘结剂，包括：
疏水性的聚醚多元醇、二异氰酸酯与具有疏水性侧链的二醇反应而成的产物。
2.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述疏水性的聚醚多元醇为1摩尔份，所述二异氰酸酯为3至20摩尔份，且所述具有疏水性侧链的二醇为1至6摩尔份。
3.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述二异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、或上述的组合。
4.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述疏水性的聚醚多元醇为聚丁二醇、聚丙二醇、或上述的组合。
5.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述具有疏水性侧链的二醇为C12-26的单脂肪酸甘油酯、C12-26的二聚脂肪酸、或上述的组合。
6.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述粘结剂的数目平均分子量大于1.6×105。
7.如权利要求1所述的用于电容去离子电极的粘结剂，其中所述疏水性的聚醚多元醇的数目平均分子量介于1000～5000之间。
8.如权利要求1所述的用于电容去离子电极的粘结剂，是用以粘结电极中的活性材料，所述活性材料为活性碳材、纳米碳管、石墨烯、或上述的组合，且所述活性材料与所述粘结剂的重量比介于90:5至90:25之间。
9.如权利要求8所述的用于电容去离子电极的粘结剂，其中所述活性材料的比表面积介于300m2/g至3000m2/g之间，且其孔洞大小介于1至1000nm。
10.如权利要求8所述的用于电容去离子电极的粘结剂，其中该电极更包含5至20重量份的导电材料，且该导电材料包括石墨、碳黑、乙炔黑、或上述的组合。
11.一种用于电容去离子电极的粘结剂的形成方法，包括：
混合疏水性的聚醚多元醇、二异氰酸酯与具有疏水性侧链的二醇，反应形成粘结剂。
12.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述疏水性的聚醚多元醇为1摩尔份，所述二异氰酸酯为3至20摩尔份，且所述具有疏水性侧链的二醇为1至6摩尔份。
13.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述二异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、或上述的组合。
14.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述疏水性的聚醚多元醇为聚丁二醇、聚丙二醇、或上述的组合。
15.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述具有疏水性侧链的二醇为C12-26的单脂肪酸甘油酯、C12-26的二聚脂肪酸、或上述的组合。
16.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述粘结剂的数目平均分子量大于1.6×105。
17.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述疏水性的聚醚多元醇的数目平均分子量介于1000～5000之间。
18.如权利要求11所述的用于电容去离子电极的粘结剂的形成方法，其中所述粘结剂是用以粘结电极中的活性材料，所述活性材料为活性碳材、纳米碳管、石墨烯、或上述的组合，且所述活性材料与所述粘结剂的重量比介于90:5至90:25之间。
19.如权利要求18所述的用于电容去离子电极的粘结剂的形成方法，其中所述活性材料的比表面积介于300m2/g至3000m2/g之间，且其孔洞大小介于1至1000nm。
20.如权利要求18所述的用于电容去离子电极的粘结剂的形成方法，其中所述电极更包含5至20重量份的导电材料，且所述导电材料为石墨、碳黑、乙炔黑、或上述的组合。
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